Chromium-containing azo dyestuffs



United States Patent 2,933,490 CHROMIUM-CONTAINING AZO DYESTUFFS Walter Biedermann, Fabio Bella, and Guido Schetty, Basel, Switzerland, assignors to J. R. Geigy A.-G., Basel, Switzerland No Drawing. Application March 12, 1959 Serial No. 798,832

Claims priority, application Switzerland April 14, 1958 7 Claims. (Cl. 260-145) Azo dyestuffs containing heavy metal which contain a monazo and a disazo dyestufi bound to a co-ordinative hexavalent heavy metal atom are described in US. patent,

application Ser. No. 635,084. These compex heavy metal compounds are suitable for the dyeing of organic materials of the most different kinds and are very valuable in particular because of their deep shades and the good fastness properties of the textile dyeings obtained therewith. The invention also concerns a process for the production of these dyestufis which consists in adding a dicyclic metallising azo dyestufi to a dicyclic co-ordinated azo dyestuff containing a co-ordinative hexavalent heavy metal atom per dyestufr molecule, the dyestuffs being so chosen that the reaction product contains a monoazo and a disazo dyestufi' bound in complex linkage at the heavy metal atom. Only those dicyclic metallising disazo dyestuffs are named which contain both azo groups at a single aromatic radical, namely bound at a benzene or naphthalene ring.

On further work being done on this subject, it has now been found that very valuable dyestuffs are also obtained if, in the process described, compounds are used as dicyclic metallising disazo dyestuffs which correspond to the formula II given below. These dyestuffs are characterised in that they consist of a metallisable monoazo dyestufi containing a non-metallisable monoazo dyestufi bound by Way of a divalent bridging member.

The new chromium-containing azo dyestuffs are obtained by reacting a metallisable monoazo dyestufl of the general formula and a metallisable disazo dyestufi of the general formula (III) with a chroming agent, the components being reacted simultaneously or one after the other and under such conditions that one molecule of the monozao dyestulf is bound by a chromium atom to one molecule of the disazo dyestufi.

The characteristic divalent bridging member X of the disazo dyestufi of the general Formula II is derived advantageously from a sulphonic acid group and is, thus, a sulphonic acid amide or a sulphonic acid ester group; it can also be derived however, from a carboxyl group and in this case it is a carboxylic acid amide group.

Two modifications of the process for the production oi these symmetrical 2:1 chromium complex compounds are available. Either somewhat more than the equimolecular amount of an agent giving off chromium is reacted with an equimolecular mixture of the metal-free monoazo and disazo dyestufis in a neutral to alkaline medium in the Warm, in which case very probably first a so-called 1:1 metal complex is formed containing a whole chromium atom to one molecule of the dyestutl, which metal complex then forms the 2:1 complex with the other metalfree dyestufl. Or, one of the two azo dyestuifs, advantageously the monoazo dyestuif, is converted into the 1:1 complex and then the second, metal-free azo dyestufi is reacted. Particularly uniform and pure 2:1 chromium complex compounds are obtained by this addition process and it is, therefore, the process preferred according to the present invention. The first process mentioned is a simplified form of the addition process; production of the 1:1 chromium complex and addition of the second dyestuif molecule are performed in the presence of the start ing materials.

in the textile dyestuifs according to the present invention, at least one of the two co-ordinated azo dyestufis contains a sulphonyl substituent which increases the water solubility. Such substituents are sulphonic acid groups, sulphonic acid amide groups or low alkyl sulphony'l groups. However, the end product advantageously contains not more than one sulphonic acid group.

The metallisable monoazo dyestuils of the general Formula I used according to the present invention are coupling products of diazonium compounds of the benzene and naphthalene series containing in the ortho-position to the diazo group a substituent capable of forming the metal complex or one which can be converted into such a group, with azo components coupling in the neighbouring position to a hydroxyl group. Metallisable groups are the carboxyl and hydroxyl groups and groups which can be converted into the latter during the metallisation reaction are, for example, the methoxy and ethoxy groups. The dyestufis can contain other substituents usual in azo dyestuffs, for example, halogen, alkyl, alkoxy, aryloxy, nitro, cyano, acyl and acylamino, alkyl and arylsulphonyl groups and carboxylic acid amide and sulphonic acid amide groups possibly further substituted at the nitrogen atom. Thus, o-carboxy, o-alkoxy and o-hydroxy diazobenzene and diazonaphthalene compounds which possibly contain the above substituents are diazo components for monoazo dyestuffs used according to the present invention. As azo components are used chiefly 4-alkylor 2.4-dialkyl or 2-acylamino-4-alkyl-1-hydroxybenzenes, also hydroxy naphthalenes such as 1- and 2-hydroxynaphthalene, l.5-, 2.6- and 2.7-dihydroxynaphthalenes or suitable substituted derivatives thereof, then pyrazolones such as l-aryl- 3 alkyl-S-pyrazolones, 1-aryl-5-pyrazolone-3-carboxylic acids andl-aryl-5-pyrazolone-3-carboxylic acid amides as well as derivatives thereof further substituted in the aryl nucleus, and finally, acylacetylamino benzenes and naphthalenes. Monoazo compounds from such diazo and azo components are known per se. They are starting materials which are often used for the production of heavy metal complex dyestuffs for W001 and material similar thereto. In the present process, chiefly the 0.0- dihyclroxymonoazo dyestuffs are used.

In the disazo dyestuffs used according to the resent invention of the general Formula II, the metalli'sable portion corresponds to the monoazo dyestutf of the general Formula I. The definition and explanation given above for these dyestufi's is also true of this part of Ithe diazo dyestuffs. The non-metallisable portion, Y-N=N-Z, can contain the most various types of components, for example, components from the benzene or naphthalene series. They can contain the substituents usual in azo dyestuffs which are listed above. The carbonyl or sulphonyl group of the bridging member X can either be bound to a component of the metallisabie or to a component of the non-metallisable portion of the disazo dyestufi.

Chiefly two methods are used for the production of the disazo dyestuffs used according to the present invention. The one consists in reacting together under suitable conditions while coupling, a metaliisable and a non-metallisable monoazo dyestuif each of which contains a reactive group. Such reactive groups are on the one hand the amino or hydroxyl groups and, for example, on the other the carboxylic acid or sulphonic acid halide groups. p a V The second, often more advantageous'method consists in reacting together either a diazo or azo component and a monoazo dyestuif each of which contains one of the previously named groups which can be coupled together and then coupling the reaction product with the remaining component to form the disazo dyestufi.

According to a preferred form of this second method, an acyloxynaphthalene sulphonic acid chloride is condensed with a non-metallisable amino or hydroxy monoazo dyestufi, the acyloxy group is saponified and the hydroxynaphthalene sulphonic acid amide or the corresponding ester is coupled in an alkaline medium with an o-carboxy or o-hydroxy benzene or naphthalene diazonium compound to form the disazo dyestuff. As acyloxynaphthalene sulphonic acid chlorides, in particular the acyl derivatives are used, for example the carbomethoxy or toluene sulphonyl derivatives of the l-hydroxynaphthalene-3- or -4-sulphonic acid chlorides which are known per se and the 2-hydroxynaphthalene4-, -5-, -6- or -7-sulphonic acid chlorides. As non-metallisable amino and hydroxy monoazo dyestuffs advantageously the easily accessible 4-aminoand 4-hydroxy azobenzenes are used. The disazo dyestuffs obtained with these components are thus the o-(arylazo)-hydroxynaphthalene sulphonic" acid-4'-benzene azo phenylamides and the o-(arylazo)-hydroxynaphthalene sulphonic acid-4-ben zene azo phenyl esters. The corresponding l-arylazo-Z- hydroxynaphthalene 3 carboxylic acid-4'-oenzene azo phenylamides are easily obtained in the same way with 2-hydroxyor- 2-acyloxy-naphthalene-3-carboxylic acid chloride.

Disazo dyestufl's according to the present invention which contain the sulphonyl group of the bridging member boundjat the diazo component of the metallisable portion are obtained, for example, by condensation of benzoxazolone sulphonic acid chlorides with 4-amino azobenzene or substitutionproducts thereof, splitting of the oxazolone ring in an alkaline medium, .diazotisation of the amino group and coupling of the diazomonoazo compound with a metallisable azo component. The 2- arylazo-1-hydroxybenzene-4- or -5-sulphonio acid-4-benzene azophenylamides for examples are obtained in this way.

Disazo dyestuffs which contain the carbonyl or sulphonyl group of the bridging member X in the nonmetallisable portion are obtained for example by condensation of azobenzene-4-carboxylic acid or sulphonic acid chloride with a hydroxybenzene or hydroxynaphthalene which contains a primary or secondary amino group and which couples in the o-position to the hydroxyl group, and coupling of the condensation product with an o-carboxy or o-hydroxy diazobenzene or diazonaphthalene compound.

The end products have advantageous properties if the disazo dyestuff containing sulphonic acid amide groups is further substituted at the amide nitrogen atom. For this purpose either amino-monoazo dyestufis correspondingly substituted at the amino group are used as starting materials or the dyestuifs containing secondary amide groups are treated with alkylating agents, for example with dialkyl sulphates or alkyl halides. V

The salts of trivalent chromium, for example chromic sulphate, chromic chloride, chromic fluoride, chron1ic 2,ee's,49o r N A acetate or chromic formiate are used as chroming agents. Also, with dyestuffs which are not sensitive to alkali, salts of hexavalent chromium can be used, for example, alkali bichromates. In this case, the presence of a reducing substance such as, e.g. glucose, is necessary. Finally, also complex chromium compounds such as chromo-salicylic acid ammonium or alkali salts can be used. To produce the 1:1 chromium complexes for the preferred addition process, the dyestuffs are treated advantageously with compounds of trivalent chromium in excess in an acid medium. Sulphonated dyestuffs are chromed advantageously in aqueous solution or suspension and unsulphonated dyestuffs in higher boiling alcohols or in the melts of amides of low fatty acids. The metallisation is performed at temperatures of -150 and, if necessary, under pressure. Particularly uniform 1:1 chromium complexes are obtained chiefly with sulphonated monoazo dyestuffs.

The metal-free azo dyestuffs are added to the 1:1 chromium complexes in a weakly acid, neutral or alkaline medium at a slightly raised temperature, for example 40-95 Theaddition is performed advantageously in aqueous or aqueous/alcoholic medium and in the pres.- ence of agents which butter the mineral acid or of alkaline agents such as, for example, sodium acetate, sodium carbonate, sodium hydroxide or the corresponding potassium or ammonium compounds. In most cases the addi tion is made quickly and completely. The new 2:1 chromium complex compounds are obtained from aqueous solutions by salting out and from alcoholic solution by precipitation with wateror by distilling off the organic solvent. e V V The new chromium-containing azo dyestuifs according to the present invention are suitable for the dyeing of organic materials ofthe most various types in orange,

brown, olive, blue, grey toviolet shades. The dyestuifs which are. insoluble in water are used principally for the dyeing of lacquers and varnishes, of paper, of viscose, nylon, cellulose ether and ester spinning masses and also of polyester condensates. 'Those which are Water soluble are chiefly textile dyestufis and are suitable in particular for the dyeing of Wool, also of casein, superpolyamide and superpolyurethane fibres and also for the dyeing of leather and furs. .The new dyestuffs can also be used for printing onto the materials mentioned. Of particular value in textile dyeing is that not only the 2:1 chromium complex dyestulfs according to the present invention containing the alkyl sulphonyl and sulphamide groups but also those containing one sulphonic acid group are distinguished by' a good neutral drawing power onto wool. The wool dyeings are very level and are distinguished by remarkable fastness to light, very good wet fastness properties, for example, very good fastness to Washing, milling and sea water, and, in many cases, also by the good fastness to alkali. In addition, the good to very good fastness to sulphur of the wood dyeings is remarkable.

Of the dyestuffs according to the present invention, principally those are valuable which correspond to the general formula In this formula:

A represents a member selected from the group consist: ing of phenylene and naphthylene radicals containing the metallised group in o-position to the azo group,

Band B each-represent a member selected from the alkyl a lkyl and -CONH-, and m and 11 each represent one of the numerals 0 and l.

A technically particularly valuable class corresponds to the general formula:

and those compounds are again preferred which correspond to the following formula B SOsH Further details can be seen from the following examples. The examples do not .limit the invention in any way but only serve to illustrate the invention. Where not expressly stated, parts are given as parts by weight and their relationship to parts by volume is as that of grammes to cubic centimetres. The temperatures are in degrees centigrade.

EXAMPLE 1 10 parts by volume of 2 N-caustie soda lye and 5.72 parts of the disazo dyestufi obtained by coupling diazotised 4-chloro-2-amino-l-hydroxybenzene with l-hydroxynaphthalene-El-sulphonic acid-N-methyl 4' benzene azo phenylamide, are added to 150 parts of water. The complex chromium compound of the type 1 atom chromiurml dyestuif molecule, which corresponds to 0.52 part of chromium and 3.94 parts of the monoazo dyestufi from 1-diazo-2-hydroxynaphthalene-4-sulphonic acid and Z-hydroxynaphthalene, is added to this mixture. The mixture is heated at 95 until the starting substances have disappeared. The chromium-containing addition dyestutf is precipitated by the addition of sodium chloride. It is filtered off and dried. After drying, it is a dark powder which dyes wool from a neutral or weakly acid bath in wet fast, reddish navy blue shades.

A dyestufi having similar properties is obtained if instead of the disazo dyestufi from diazotised 4-chloro-2- amino-l-hydroxybenzene and l-hydroxynaphthalene-3- sulphonic acid-N-methyl-4-benzene azo I phenylamide, 6.06 parts of the disazo dyestufi from 4chloro-2-amino-1- hydroxybenzene and 1-hydroxynaphthalene-3-sulphonic acid-N-methyl4'-(4"-chlorobenzene azo)-phenylamide is used.

EXAMPLE 2 terials have disappeared. The chromium complex formed I is precipitated by the addition of sodium chloride, filtered off and dried. After drying, .it is a dark powder which dyes wool from a neutral or weakly acid bath in reddish navy blue shades. The wool dyeing is good wet fastness properties.

distinguished by HOaS- 10 parts by volume of 2 N-cau stic soda lye and 5.37 parts of the disazo dyestufi from diazotised Z-amino-lhydroxybenzene-S-sulphonic acid-N-methyl-4-benzene azo phenylamide and Z-hydroaynaphthalene are added to 150 parts of Water. The complex chromium compound of the type 1 chromium atomzl dyestufi molecule which 1" corresponds to 0.52 part of chromium and 3.94 parts of the dyestufi from 1-diazo-2-hydroxynaphthalene-4-sulphonic acid and Z-hydroxynaphthalene is also added.

. The mixture is heated to 90-95 and kept at this temperature until the starting substances have disappeared.

The new chromium-containing dyestufi is precipitated by the addition of sodium chloride, filtered off and dried. After drying, it is a dark powder which dyes wool from a neutral or weakly acid bath in fast grey-blue shades.

EXAMPLE 4 51pm of the disazo dyestufi from diaz otised S-nitrodyestulf from 4-chloro-2-amino-l-hydroxyb'enzene and}- hydrorrynaphthalene tS-Sulphonic acid, and 1.8; parts of "sodium carbonate are suspended in 159 "parts of water. The mixture is heated to"6065 and kept'at thistem- HOIS ' EXAMPLE 5 2 parts of crystallised sodium acetate and-5.22 parts of the disazo dyestufi from diazotised 4-chloro-2 amino-L hydroxybenzene and 2-hydroxynaphthalenee3-carboxylie acid-4'-benzene azo phenylamide are added to 200 parts of aqueous 50% ethanol. Also the complex chromium compound the type 1 chromium atomz'l dyestufi molecule which corresponds to 0.52 part of chromium and 3.94 parts of the monoazo dyestuff from 'l-diazo-Z-hydroxynaphthalene-4-sulphonic acid and Z-hydroxynaphthalene is added. The mixture is warmed to 70-75 until the starting substances have disappeared. The alcohol is then distilled OE and the reaction mixture is evaporated to dryness. The dyestuff is a dark powder. It dyes wool from a neutral or weakly acid bath in a fast grey shade.

EXAMPLE 6 1.8 parts of sodium carbonate and 6.39 parts of the disazo dyestufi from diazotised 4-chloro-2-amino-1-hydroxybenzene and l-hydroxynaphthalene-3-sulphonic acid- 4-(4-sulphobenzene-azo)-phenylester are added to 150 parts of Water. The complex chromium compound of the type lchromium atomal dyestufi molecule which corresponds to 0.52 part of chromium and 3.99 parts of the monoazo dyestufi from 4-chloro-2-an1ino-l-hydroxyben- "7 5 zene and 2-hydroxynaphthalene is then added. The mixis heated to 6.0 615 and keptat this temneramre until the starting substances, have disappeared. The new chromium-containing dyestufi is precipitated by the addition of sodium chloride and isolated according to the usual methods. After drying, it is a dark powder which dyes wool in violet-blue shades. The dyeings have good fastness properties.

EXAMPLE 7 N O, CsHu Hoes N=N 10 parts by volume of 2 N-caustic soda lye and 5.72 parts of the disazo dyestufi from diazotised 4-chIoro-2- amino-l-hydroxybenzene and 2-hydroxynaphthalene-6- sulphonic acid-N-methyl-4'-benzene azo phenylamide are added to 150 parts of water. The complex chromium compound of the type 1 chromium atomzl dyestufi molecule which corresponds to 0.52 part of chromium and 4.09 parts of the monoazo dyestuif from 4-nitro-2- aminorl-hydroxybenzene-6-S111Phonic acid and 4-amyl-1 hydroxybenzene is, then added. The mixture is heated at 90-95 and held at this temperature until the starting substances have disappeared. The new chromiumcontaining addition dyestulf' is precipitated by the. addition of sodium chloride and filtered H and dried. After drying it is a dark powder which dyes wool from a neutral or weakly acid bath in a fast brown, Shade- EXAMPLE 8 5.83 parts of the disazo dyestufi' from dinotised. 6..-.

10 'naphthalene-i-sulphonic: acid-4'-benzene azo phem/l ester, also 4.44- parts of the complex chromium compound of the type 1 chromium atom:1 dyestutf molecule which corresponds to 0.52 part-of chromium and 3.94 parts of the monoazo dyestufi from 1-diazo-2-hydroxynaphthalene-- 4-sulphonic acid and 2-hydroxynaphtha1ene, and 1.8 parts of sodium carbonate are added to 150 parts of water.

The mixture is heated at -65 until the starting substances have disappeared. The chromium complex formed is. precipitated by the addition of sodium chloride, filtered off and dried. After drying, it is a dark powder which dyes wool from a neutral to weakly acid bath in wet fast, blue shades which have good fastness to light.

EXAMPLE 9 01 SO IE Cl N=N N H-C O-C H:

I OgN- N=N 6.05 parts of the sodium salt of the disazo dyestufi from diazotised 6-nitro-4-methyl-2-amino 1 hydroxybenzene and 1-hydroxynaphthalene-3-sulphonic acid-4-benzene azo. phenyl ester, also 5.27 parts of the sodium salt of the nitro-2-amino-4-methylrl-hydroxybenzene and l-hydroxy- T1 '2 parts of crystallised sodiumacetate and 5.15 parts oi the disazo dyestuff from diazotised Z-aminobenzenel-carboxylic acid and 2-hydroxynaphthalerie-3-carboxylic acid-4-benzene azo phenylamide are added to 150 parts of ethanol. Also the complex chromium compound of the type 1 chromium atom:1 dyestufi molecule which corresponds to 0.52 part of chromium and 4.07 parts of the monoazo dyestuif from 2-amino-l-hydroxybenzene- 4-methyl sulphone and 1-(3-chloro)-phenyl-3-methyl-5= pyrazolone is added. The mixture is heated at 70-75 until no more starting materials are present. The alcohol is then distilled off and the reaction mixture is evaporated to dryness. The dyestufi is a powder which dyes wool from a neutral or weakly acid bath in fast, brown- 2 parts of crystallised sodium acetate and 5.24 parts of the disazo dyestuff from diazotised 4-nitro-2-aminol-hydroxybenzene and 4-methyl-2-(4-benzene azo benzoyl-N-ethylamino)-1-hydroxybenzene are added to 200 12 parts of aqueous ethanol. Also the complexchromium compound of the type 1 chromium atom: I dyes'tufi molecule corresponding to 0.52 part of chromium and 4.09 parts of the monoazo dyestufi from 4-nitro-2- amino-1-hydroxybenzene-6-sulphonic acid and 4-amyl-l- 'hydr'oxybenzene is added. The mixture is warmed to 75 until the starting substances have disappeared. The alcohol is then distilled ofi and the reaction mixture is evaporated to dryness. The dyestufi is a dark powder. It dyes wool from a neutral or weakly acid bath a fast brown shade.

EMMPLE 12 EXAMPLE 13 4 parts of the chromium-containing dyestuff according to Example 8 are dissolved in 4000 parts of water. parts of previously well wetted wool are entered at 40- 50. 2 parts of 40% acetic acid are added and the bath is brought to the boil within half an hour and kept for 45 minutes at boiling temperature. The wool is then rinsed with cold Water and dried. The navy blue wool dyeing has good fastness properties.

A-wool dyeing having similar properties is also obtained if dyeing. isperformed in a, liquor containing GIaub'efissalt. I The following table contains other dyestuffs according to the present invention which are obtained by using the methods described in the above examples.

. Table Monoazo dyestufi.

Shade of wool Disazo dyestufi dyeing '4-sulphonlc acl 1 droxynaphthalene (3.94 parts).

5-nitro-2- a m in o 1 b y droxybenezne grey blue.

1-hydroxynaphtha1ene-3- sulphonic acid 4 benzene azo phenyl ester (5.7 parts). 7 4- chloro -2 amino 1 -hydroxybenzene navy blue.

4 ehloro -2 amino 1 hydroxybenzene navy blue.

1 hydroxynaphthalene 3 sulphonic acid-4-(4-chlorobenzene azo)-phenyl ester (5.93 pts.). 4-chloro-2-amino-1 -h vdroxybenzene 1 hydroxynaphthalene 3 sulphonie acid-4 (4"-methoxybeuzeue azo) -pheny1 ester (5.89 pts.). 4-chloro-2-amino-l-hydroxybenzene 1 hydroxynaphthalene 3 sulphonic acid- 4 (2 -metbylbenzene azo)-phenyl'ester (5.73 parts). 4 -chloro -2-amino 1 -hydroxybenzene 1 hydroxynaphthalene 3 sulpbonie acid -4 (2.6" dimethyl benzene azo)-phenyl ester (5.87 pts.).' 5 -nitro 2 amino 1 hydroxyb enzene 2 hydroxvnaphthalene 3 carboxylic acid-4-hen1.ene azo phenyl amide (5.32 parts). 6-nitro-4-methyl-2-amino-1-hydroxybenzene 2-hydroxynaph-' thalene-3-carboxylic acid-4-benzene azo phenylamide (5.46 pts.). 4- ehloro -2-amino-1-hydroxybenzene 2 hydroxynaphthalene 3 carboxylic acid-N-methyl-4-benzene azo pbenylamide (5.36 pts.). v 4-chloro 2- amino 1 -7hydroxybenzene Do.

I and benzoy1amin0)-naphtha1ene (5.22 parts).

Table-Continued No. Monoazo dyestufl Disazo dyestufi Shade of wool dyein 41 2-amir1o-1-hydroxybenzene-4-sulphonic 2-amino-l-hydroxybenzene-S-sulphonic reddish orange.

acid 1-(3'-chloro)-phcnylacid-N-methy1-4-benzene azo phen- 3-methyl-5-pyrazolone (4.09 parts). ylamide 1-phenyl-3-methyl- 5-pyrazo1one (5.67 parts). 42 1-diazo-2-hydroxynaphthalene-4-sul- 4-chloro-2-amino-l-hydroxybenzene reddish blue.

phonic acid'- Z-hydroxynaphz-hydrownaphthaIene-G-sulthalene (3.94 parts). phonic acid-4-benzene azo phenyl ester (5,5 9 pts.). 43 do 4-ehloro-2-amino-1-hydroxybenzene Do.

2-hydroxynaphthalene'6-sul' phonic acid-N-methyl4-(2-methoxyenzeue azo phenylamide (6.02 per s a t l 44 (in 4-chloro-2-arnino-1-hydroxybenzeue Do.

2-11ydroxynaphthalene-ti'sulphonic acid-N-ethyl-4'-benzene a zo V W phenylamide (6.16 parts). 45 6-nitro-4-methyi-2-ernino-l-hydroxyblue.

benzene 2-hydro rynaphthaleneefi-sulphom'c acid-4'-benzene azo v phenyl e ter (6.05 parts). 7 46..---- 2-am1no-1-hydroxybenzene-4-methyl- Z-amino-l-hydroxybenzene-4-phenyl red brown.

sulphone l-phenybS-methylsulphone l-hydroxynaphfi-pyrazolone (3.72 pts.). thalene-3-sulphonic acid-4-benzene azo phenyl ester (6.64 parts). 41..-.-. 2 amino 1 hydroxybenzene 4 suldn Do.

phonic acid amide l-phenyl- 7 B-methyl-S-pyrazolone (3.73 parts). l v .7 a 48..-.--. 2-amino-l-hydroxybenzene-i-rnethyl Z-aminobenzene-l-carboxylic acid-5- brown violet.

sulphone Z-hydroxynaphsulphonic acid amide 2 hythelene (3.42 parts). 7 droxynaphthalene-3-carboxylic acid- 4'-bar;zene azo phenylarnide (5.94

par 5 r r 49 4-chloro-2-aminobenzene-l-carboxylic 6-nitro-4-methil-2omino-l-hydroxyyellowish olive.

acid l-(4'sulphonic acid)- benzene V- l-hydroxynaphthaphen l-3-methyl-5-pyrazolone (4.37 'lene-3-su lphonic acid-4-benzene azo parts phenyl ester (5.83 parts).

What we claim is:

1. The complex chromium compound of the general; 5

formula wherein:

- wherein:

- A represents a member selected from the grouptconsisting represents a member selected from the group consisting of phenylene and naphthylene radicals containing the metallised group in o-position to the azo group, B and E each represent a naphthylene radical containing the 50 Y F 60 2. The complex chromium compound of thegeneral of phenylene and naphthylene radicals containing the metallised group in o-position to the am group, B represents a naphthylene radical containing the metallisted group in o-position to the azo group, and D represents a phenylene radical containing the metallised group in o-position to the am group.

3. A complex chromium compound of the formula sour 17 18 4. A complex chromium compound of the formula 6. The complex chromium compound of the formula NzzN- 7. The complex chromium compound of the formula 5. The complex chromium compound of the formula 25 SOsH o I o TN References Cited in the file of this patent UNITED STATES PATENTS 2,559,331 Widmer et a1. July 3, 1951 

1. THE COMPLEX CHROMIUM COMPOUND OF THE GENERAL FORMULA 